CN107189061A - A kind of Halogen melt-drip resistant inflaming retarding nylon 6 resin and preparation method thereof - Google Patents

A kind of Halogen melt-drip resistant inflaming retarding nylon 6 resin and preparation method thereof Download PDF

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CN107189061A
CN107189061A CN201710349417.2A CN201710349417A CN107189061A CN 107189061 A CN107189061 A CN 107189061A CN 201710349417 A CN201710349417 A CN 201710349417A CN 107189061 A CN107189061 A CN 107189061A
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nylon
resin
inflaming retarding
pressure
preparation
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CN107189061B (en
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李发学
范硕
吴德群
王学利
俞建勇
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Jiahua Special Nylon Jiangsu Co ltd
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Donghua University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups

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Abstract

The present invention relates to a kind of Halogen melt-drip resistant inflaming retarding nylon 6 resin and preparation method thereof, structural formula is：

Description

A kind of Halogen melt-drip resistant inflaming retarding nylon 6 resin and preparation method thereof
Technical field
The invention belongs to flame-retarded resin and its preparation field, more particularly to a kind of Halogen melt-drip resistant inflaming retarding nylon 6 resin and Its preparation method.
Background technology
Nylon 6 is that a kind of burning velocity is fast, and the high high polymer material of heat release amount can also discharge in combustion in addition A large amount of dense smokes and with the phenomenon of molten drop, can be caused serious injury to human body and ecological environment.Current numerous researchers In order to improve the combustibility of nylon 6, many research work have been done, it is also just gradually good to environmental protection, combination property Direction is developed.
Patent CN 104311877A are related to a kind of response type nylon fire retardant and preparation method, it is characterised in that：Halogen contains Phosphorus copoly type fire retardant elder generation and diol reaction, obtain fire-retardant esterifying liquid；Then halogen-free phosphorus-containing nylon is obtained with binary acid reaction Fire retardant.The resistance to 250 DEG C of high temperature of fire retardant that the present invention is obtained, limited oxygen index more than 30%, UL94 indexes up to V-0 grades with On, and with permanent fire retardant effect.
The A of patent CN 103351605 disclose a kind of Green environment-friendlyflame-retardant flame-retardant nylon, with phosphorus nitrogen composite halogen-free polymer, Methyl phenyl siloxane branched chain type prepolymer, carries out flame retardant treatment to nylon 6 with reference to the nano combined environmental protection fire retarding agent of antimony base, prepares Go out high comprehensive performance, without halogen, low cigarette, environmentally friendly flame retardant type nylon 6 resin.
The A of patent CN 105482448 disclose a kind of heat and flame resistant nylon tubing, and it is by nylon 6, poly- methyl hydrogen silica Alkane, epoxy resin, titanate coupling agent modified nano zine oxide, modified acicular wollastonite, amination CNT, nanometer titanium dioxide Silicon, aluminum diethylphosphinate, Lanthanum Stearate etc. are blended.Heat and flame resistant nylon tubing is prepared, its heat resistance and good flame resistance, by force Degree is high, and excellent shock resistance, the nylon tube good combination property being made of it, service life is long.
As can be seen here, fire retardant is added to the flame retardant products of nylon 6 with copolymerized form in fire-retardant Nylon 6 field at present, Generally using phosphate as the main body of fire retardant, the fire retardant such as nitrogen system, silicon systems, metal is as assisting flame-resistant material, but phosphorus system Fire retardant can produce the poisonous intermediate product such as phosphoric acid, metaphosphoric acid in combustion, will necessarily produce in use negative The influence in face.And the fire proofing prepared with blending method, in order to reach preferable flame retardant effect, the addition of fire retardant compared with Greatly, nylon 6 material mechanical property will necessarily be caused to decline to a great extent.Therefore mechanical property and fire resistance requirement are taken into account, it is simultaneously full The key of demand, necessarily fire retardant and flame-retarded resin Future Development that toe ring is protected.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of Halogen melt-drip resistant inflaming retarding nylon 6 resin and its preparation side Method, carries out the esterification formation carboxylate of nylon 6 by a kind of performed polymer of nylon 6 of carboxy blocking and glycol, is then made with reaction Pure silicon system flame retardant oligomer carry out the process of ester exchange reaction, and then synthesize that flame retardant effect is good and environmentally friendly nothing of anti-dropping Malicious nylon 6 resin.
A kind of Halogen melt-drip resistant inflaming retarding nylon 6 resin of the present invention, the structure of the Halogen melt-drip resistant inflaming retarding nylon 6 resin Formula
For：
Wherein 2≤m≤5,5≤n≤40,10≤p≤30.
A kind of preparation method of Halogen melt-drip resistant inflaming retarding nylon 6 resin of the present invention, including：
Prepare the fire-retardant oligomer of silicon systems of environmental protection：
(1) by weight, by 10 parts of diphenyl silanediol DPSD, 0.05~0.25 part of catalyst, l0 parts of organic solvents Mixed dissolution, then reacts under the conditions of 25~80 DEG C, 50~800Pa of pressure, phenyl silicone is obtained after question response is complete PDPS；
Prepare the carboxylate of nylon 6：
(2) by weight, 100 parts of caprolactams, 1~10 part of ring opening agent, 0~5 part are helped into ring opening agent and 1~20 part is sealed End agent is added in reactor, is passed through nitrogen 3~6 times until air is replaced in kettle, and possesses 0.02~0.1MPa pressure Power, then raises temperature to 220~260 DEG C, 2~3h of stirring reaction；Then pressure in kettle is adjusted to 50~400Pa, in 200~ 240 DEG C are continued to react 1~2h, obtain the PA6 prepolymers of the end carboxyl of certain molecular weight；
(3) pressure is normal pressure in regulation kettle, and it is normal pressure that ought adjust pressure in kettle by secondary charging device, by 1-10 parts Ethylene glycol is added in the PA6 prepolymers of 100 parts of end carboxyls, is discharged, is obtained after 0.5~2h of reaction under the conditions of 220~260 DEG C The carboxylate of low molecule amount nylon 6；
Prepare fire-retardant Nylon 6 resin：
(4) 100 parts of carboxylates of nylon 6, PDPS, 0.5-1.5 parts of ester exchange catalysts of 15-40 parts of phenyl silicones are added Enter in reaction vessel, be passed through nitrogen displacement tainer air, reacted at 160~200 DEG C after 3~5h, in regulation reaction vessel Pressure is 0~200Pa, continues to react 3~5h, produces Halogen melt-drip resistant inflaming retarding nylon 6 resin.
Catalyst is inorganic acid or lewis acid catalyst in the step (1).
The inorganic acid is hydrochloric acid, sulfuric acid, perchloric acid；Lewis acid catalyst be zinc chloride, sodium chloride, iron chloride, One kind in aluminium chloride, stannic chloride.
The reaction time is 6-72h in the step (1).
Organic solvent is one in toluene, tetrahydrofuran, N, N dimethyl pyrrolidones, dioxane in the step (1) Kind.
Ring opening agent is water in the step (2)；It is aminocaproic acid to help ring opening agent；End-capping reagent is adipic acid.
Ester exchange catalyst is butyl titanate, isopropyl titanate, zinc acetate, manganese acetate, three oxidations in the step (4) One kind in two antimony.
The carboxylate segment of nylon 6 of end group esterification, its molecular weight ranges is 500~2000g/mol, accounts for whole copolymer and rubs The 50%~75% of that total amount；The siloxanes of fire-retardant segment, its molecular weight ranges are 200~1000g/mol, account for copolymer mole The 25%~50% of total amount.
The preparation method of a kind of Halogen melt-drip resistant inflaming retarding nylon 6 resin of the present invention, by by the pre-polymerization of both-end carboxyl nylon 6 Thing, the carboxylate of esterification formation nylon 6 is carried out with glycol, then with the silicon systems flame-retardant monomer of terminal hydroxy group, carries out ester exchange Fire-retardant Nylon 6 resin is prepared in reaction.Silicon systems flame-retardant monomer and fire-retardant Nylon 6 resin structure formula are as follows：
Phenyl silicone structural formula is：
Wherein 2≤m≤5.
Fire-retardant Nylon 6 resin copolymer synthesizes equation：
Wherein 2≤m≤5,5≤n≤40,10≤p≤30.
Fire-retardant Nylon 6 resins synthesis route
Obtained reaction-type flame-retarding nylon 6 resin mechanical property and hot property are all close to pure nylon 6 in the present invention, and have The features such as having high flame retarding efficiency, anti-dropping.
The present invention first reacts diphenyl silanediol, acid catalyst and organic solvent, phenyl siloxane is made oligomeric Thing；Nylon polymerization monomer caprolactam, ring opening agent and end-capping reagent are added among reactor simultaneously and carry out ring-opening polymerization, And with the glycol fat polymerization that is subsequently added, so that the carboxylate of nylon 6 is made；Then will the obtained carboxylate of nylon 6 of reaction, benzene Radical siloxane oligomer and ester exchange catalyst are placed in four-hole boiling flask, and fire-retardant Nylon 6 resin is made in end reaction.
Beneficial effect
The present invention phenyl siloxane is introduced into the agent structure of nylon 6 in the way of chemical copolymerization so that fire retardant with The perfect adaptation of nylon 6, will not only have a negative impact to the mechanical performance of nylon 6, on the contrary assign the environmental protection of nylon 6, While anti-dropping performance, nylon 6 obtains better more longlasting flame retardant effect；
The UL94 indexes of the fire-retardant Nylon 6 of the present invention are V-0 ranks, light in rear 30s self-gravitation without molten drop phenomenon, resin The elongation at break of film is 20~26%, and fracture strength is 35~45MPa.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited Scope.
Embodiment 1
(a) the fire-retardant oligomer of silicon systems of environmental protection is prepared
10g diphenyl silanediols (DPSD), 0.135gHCl and 50ml tetrahydrofurans (THF) is weighed to fill in three-necked flask Divide dissolving.Stirred under conditions of 25 DEG C, 800Pa, react 60 hours, after question response is complete, obtain product phenyl silicone (PDPS, m ≈ 4).
(b) carboxylate of nylon 6 is prepared
The first step：100g caprolactams, 5g water, 1g aminocaproic acids and 16.75g adipic acids are added in reactor, led to Enter nitrogen 3 times until air is replaced in kettle, and possesses 0.025MPa pressure, then raise temperature to 260 DEG C, stirring reaction 2 Hour；Pressure in kettle is adjusted to 400Pa, in continuing to react 2 hours at 220 DEG C, the end carboxyl that molecular weight is 1000 is obtained PA6 prepolymers.
Second step：After first step reaction terminates, pressure is normal pressure in regulation kettle, is added by secondary charging device 7.96g ethylene glycol, reaction discharges after 1 hour at 220 DEG C, that is, obtains the carboxylate of nylon 6 of low molecule amount.
(c) fire-retardant Nylon 6 resin is prepared
The obtained carboxylate of 100g nylon 6,30g PDPS and 1g zinc acetates are put into four mouthfuls of glass flasks, nitrogen is passed through Gas is replaced to react 3 hours at air in bottle, 180 DEG C, and then the regulation pressure in the bottle is 200Pa, and continuation is reacted 3 hours, final To the good fire-retardant Nylon 6 resin of Halogen anti-dropping combination property (p ≈ 20).The UL94 indexes of gained nylon 6 resin are promoted to V-0 ranks, light rear 17s self-gravitations without molten drop phenomenon, the elongation at break of resin film is 25%, fracture strength 38MPa.
Embodiment 2
(a) the fire-retardant oligomer of silicon systems of environmental protection is prepared
Weigh 10g diphenyl silanediols (DPSD), 0.18g H2SO4And 50ml N, N dimethyl pyrrolidones (NMP) is in three Fully dissolved in mouth flask.Stirred under conditions of 80 DEG C, 200Pa, react 8 hours, after question response is complete, obtain product polyphenyl Radical siloxane (PDPS, m ≈ 4)).
(b) carboxylate of nylon 6 is prepared
The first step：100g caprolactams, 2g water, 4g aminocaproic acids and 7.8g adipic acids are added in reactor, are passed through Nitrogen 3 times then raises temperature to 260 DEG C, stirring reaction 2 hours until air is replaced in kettle, and possesses 0.2MPa pressure； Pressure in kettle is adjusted to 200Pa, in continuing to react 2 hours at 240 DEG C, the end carboxyl PA6 that molecular weight is 2000 is obtained pre- Polymers.
Second step：After first step reaction terminates, pressure is normal pressure in regulation kettle, is added by secondary charging device 3.97g ethylene glycol, reaction discharges after 1 hour at 260 DEG C, that is, obtains the carboxylate of nylon 6 of low molecule amount.
(c) fire-retardant Nylon 6 resin is prepared
The obtained carboxylate of 100g nylon 6,15g PDPS and 0.5g butyl titanates are put into four mouthfuls of glass flasks, The interior air of nitrogen displacement bottle is passed through, 200 DEG C of lower reaction 4 hours then adjusts the pressure in the bottle for 200Pa, continues reaction 3 small When, finally give the good fire-retardant Nylon 6 resin of Halogen anti-dropping combination property (p ≈ 15).The UL94 of gained nylon 6 resin refers to Number is V-0 ranks, lights rear 25s self-gravitations without molten drop phenomenon, the elongation at break of resin film is 24%, fracture strength 44MPa.
Embodiment 3
(a) the fire-retardant oligomer of silicon systems of environmental protection is prepared
Weigh 10g diphenyl silanediols (DPSD), 0.5g AlCl3And 50ml toluene fully dissolves in three-necked flask. 50 DEG C, stir under conditions of 100Pa, react 8 hours, after question response is complete, obtain product phenyl silicone (PDPS).
(b) carboxylate of nylon 6 is prepared
The first step：100g caprolactams, 4g water, 2g aminocaproic acids and 21.72g adipic acids are added in reactor, led to Enter nitrogen 3 times until air is replaced in kettle, and possesses 0.05MPa pressure, then raise temperature to 240 DEG C, stirring reaction 2 is small When；Pressure in kettle is adjusted to 300Pa, in continuing to react 2 hours at 240 DEG C, the end carboxyl PA6 that molecular weight is 800 is obtained Prepolymer.
Second step：After first step reaction terminates, pressure is normal pressure in regulation kettle, is added by secondary charging device Discharged after 9.23g ethylene glycol, 240 DEG C of lower reaction 2 hours, that is, obtain the carboxylate of nylon 6 of low molecule amount.
(c) fire-retardant Nylon 6 resin is prepared
The obtained prepolymer of 100g nylon 6,38g PDPS and 0.8g manganese acetates are put into four mouthfuls of glass flasks, are passed through Air in nitrogen displacement bottle, reacts 4 hours at 160 DEG C, and then the regulation pressure in the bottle is 50Pa, continues to react 3 hours, final To the good fire-retardant Nylon 6 resin of Halogen anti-dropping combination property (p ≈ 28).The UL94 indexes of gained nylon 6 resin are V-0 grades Not, rear 13s self-gravitations are lighted without molten drop phenomenon, the elongation at break of resin film is 22%, fracture strength 36MPa.
Embodiment 4
(a) the fire-retardant oligomer of silicon systems of environmental protection is prepared
10g diphenyl silanediols (DPSD), stannic chloride and 50ml dioxane is weighed fully to dissolve in three-necked flask. 60 DEG C, stir under conditions of 100Pa, react 8 hours, after question response is complete, obtain product phenyl silicone (PDPS, m ≈ 4))。
(b) carboxylate of nylon 6 is prepared
The first step：100g caprolactams, 3g water, 3g aminocaproic acids and 10.64g adipic acids are added in reactor, led to Enter nitrogen 3 times until air is replaced in kettle, and possesses 0.05MPa normal pressure, then raise temperature to 240 DEG C, stirring reaction 2 Hour；Pressure in kettle is adjusted to negative pressure 300Pa, in continuing to react 2 hours at 220 DEG C, the end carboxylic that molecular weight is 1500 is obtained Base PA6 prepolymers.
Second step：After first step reaction terminates, pressure is normal pressure in regulation kettle, is added by secondary charging device 4.52g ethylene glycol, reaction discharges after 2 hours at 240 DEG C, that is, obtains the carboxylate of nylon 6 of low molecule amount.
(c) fire-retardant Nylon 6 resin is prepared
The obtained prepolymer of 100g nylon 6,20g PDPS and 1.5g isopropyl titanates are put into four mouthfuls of glass flasks, Reaction 4 hours at air in nitrogen displacement bottle, 160 DEG C are passed through, then the regulation pressure in the bottle is 50Pa, continues reaction 3 hours, most The good fire-retardant Nylon 6 resin of Halogen anti-dropping combination property (p ≈ 20) is obtained eventually.The UL94 indexes of gained nylon 6 resin are V-0 ranks, light rear 21s self-gravitations without molten drop phenomenon, the elongation at break of resin film is 23%, fracture strength 40MPa.
Embodiment 5
(a) the fire-retardant oligomer of silicon systems of environmental protection is prepared
10g diphenyl silanediols (DPSD), 0.41g perchloric acid and 50ml tetrahydrofurans (THF) are weighed in three-necked flask Fully dissolving.Stirred under conditions of 25 DEG C, 800Pa, react 72 hours, after question response is complete, obtain experimental product polyphenylene Siloxanes (PDPS, m ≈ 5)).
(b) carboxylate of nylon 6 is prepared
The first step：100g caprolactams, 5g water, 1g aminocaproic acids and 13.62g adipic acids are added in reactor, led to Enter nitrogen 3 times until air is replaced in kettle, and possesses 0.025MPa pressure, then raise temperature to 260 DEG C, stirring reaction 2 Hour；Pressure in kettle is adjusted to 400Pa, in continuing to react 2 hours at 220 DEG C, the end carboxyl that molecular weight is 1200 is obtained PA6 prepolymers；
Second step：After first step reaction terminates, pressure is normal pressure in regulation kettle, is added by secondary charging device 5.78g ethylene glycol, reaction discharges after 1 hour at 220 DEG C, that is, obtains the carboxylate of nylon 6 of low molecule amount；
(c) fire-retardant Nylon 6 resin is prepared
The obtained carboxylate of 100g nylon 6,25g PDPS and 1.2g antimony oxides are put into four mouthfuls of glass flasks, It is passed through at air in nitrogen displacement bottle, 190 DEG C and reacts 3 hours, then the regulation pressure in the bottle is 200Pa, continues to react 3 hours, Finally give the good fire-retardant Nylon 6 resin of Halogen anti-dropping combination property (p ≈ 24).The UL94 indexes of gained nylon 6 resin V-0 ranks are promoted to, rear 18s self-gravitations are lighted without molten drop phenomenon, the elongation at break of resin film is 26%, fracture strength 40MPa。
Embodiment 6
(a) the fire-retardant oligomer of silicon systems of environmental protection is prepared
Weigh 10g diphenyl silanediols (DPSD), 0.52g ZnCl2And 50ml toluene fully dissolves in three-necked flask. Stirred under conditions of 25 DEG C, 800Pa, react 48 hours, after question response is complete, obtain experimental product phenyl silicone (PDPS, m ≈ 3)).
(b) carboxylate of nylon 6 is prepared
The first step：100g caprolactams, 5g water, 1g aminocaproic acids and 8.73g adipic acids are added in reactor, are passed through Nitrogen 3 times then raises temperature to 260 DEG C, stirring reaction 2 is small until air is replaced in kettle, and possesses 0.025MPa pressure When；Pressure in kettle is adjusted to 400Pa, in continuing to react 2 hours at 220 DEG C, the end carboxyl PA6 that molecular weight is 1800 is obtained Prepolymer.
Second step：After first step reaction terminates, pressure is normal pressure in regulation kettle, is added by secondary charging device 3.76g ethylene glycol, reaction discharges after 2 hours at 220 DEG C, that is, obtains the carboxylate of nylon 6 of low molecule amount.
(c) fire-retardant Nylon 6 resin is prepared
The obtained carboxylate of 100g nylon 6,17g PDPS and 1.2g isopropyl titanates are put into four mouthfuls of glass flasks, It is passed through at air in nitrogen displacement bottle, 200 DEG C and reacts 4 hours, then the regulation pressure in the bottle is 100Pa, continues to react 2 hours, Finally give the good fire-retardant Nylon 6 resin of Halogen anti-dropping combination property (p ≈ 18).The UL94 indexes of gained nylon 6 resin V-0 ranks are promoted to, rear 24s self-gravitations are lighted without molten drop phenomenon, the elongation at break of resin film is 22%, fracture strength 45MPa。
Embodiment 7
(a) the fire-retardant oligomer of silicon systems of environmental protection is prepared
Weigh 10g diphenyl silanediols (DPSD), 0.23g NaCl and 50ml dioxane fully molten in three-necked flask Solution.Stirred under conditions of 25 DEG C, 800Pa, react 48 hours, after question response is complete, obtain experimental product phenyl silicone (PDPS, m ≈ 3)).
(b) carboxylate of nylon 6 is prepared
The first step：100g caprolactams, 4g water, 2g aminocaproic acids and 9.9g adipic acids are added in reactor, are passed through Nitrogen 3 times then raises temperature to 260 DEG C, stirring reaction 2 is small until air is replaced in kettle, and possesses 0.025MPa pressure When；Pressure in kettle is adjusted to 400Pa, in continuing to react 2 hours at 220 DEG C, the end carboxyl PA6 that molecular weight is 1600 is obtained Prepolymer.
Second step：After first step reaction terminates, pressure is normal pressure in regulation kettle, and by secondary charging device, is added 4.21g ethylene glycol, reaction discharges after 2 hours at 220 DEG C, that is, obtains the carboxylate of nylon 6 of low molecule amount.
(c) fire-retardant Nylon 6 resin is prepared
The obtained carboxylate of 100g nylon 6,19g PDPS and 1g isopropyl titanates are put into four mouthfuls of glass flasks, led to Enter reaction 4 hours at air in nitrogen displacement bottle, 195 DEG C, then the regulation pressure in the bottle is 100Pa, continues reaction 2 hours, most The good fire-retardant Nylon 6 resin of Halogen anti-dropping combination property (p ≈ 18) is obtained eventually.The UL94 indexes of gained nylon 6 resin are carried V-0 ranks are risen to, rear 22s self-gravitations are lighted without molten drop phenomenon, the elongation at break of resin film is 20%, fracture strength 42MPa.

Claims (8)

1. a kind of Halogen melt-drip resistant inflaming retarding nylon 6 resin, it is characterised in that：The knot of the Halogen melt-drip resistant inflaming retarding nylon 6 resin Structure formula is：Wherein 2≤m≤5,5≤n≤40,10≤ p≤30。
2. a kind of preparation method of Halogen melt-drip resistant inflaming retarding nylon 6 resin as claimed in claim 1, including：
(1) by weight, 10 parts of diphenyl silanediol DPSD, 0.05~0.25 part of catalyst, l0 parts of organic solvents are mixed Dissolving, then reacts under the conditions of 25~80 DEG C, 50~800Pa of pressure, obtains phenyl silicone PDPS；
(2) by weight, 100 parts of caprolactams, 1~10 part of ring opening agent, 0~5 part are helped into ring opening agent and 1~20 part of end-capping reagent It is added in reactor, is passed through nitrogen until air is replaced in kettle, and possesses 0.02~0.1MPa pressure, subsequent heating To 220~260 DEG C, 2~3h of stirring reaction；Then pressure in kettle is adjusted to 50~400Pa, continues to react in 200~240 DEG C 1~2h, obtains the PA6 prepolymers of end carboxyl；
(3) pressure is normal pressure in regulation kettle, by the PA6 prepolymers of 1-10 part ethylene glycol 100 parts of end carboxyls of addition, 220 React after 0.5~2h and discharge under the conditions of~260 DEG C, obtain the carboxylate of nylon 6；
(4) 100 parts of carboxylates of nylon 6, PDPS, 0.5-1.5 parts of ester exchange catalysts of 15-40 parts of phenyl silicones are added anti- Answer in container, be passed through nitrogen displacement tainer air, reacted at 160~200 DEG C after 3~5h, pressure in regulation reaction vessel For 0~200Pa, continue to react 3~5h, produce Halogen melt-drip resistant inflaming retarding nylon 6 resin.
3. a kind of preparation method of Halogen melt-drip resistant inflaming retarding nylon 6 resin according to claim 2, it is characterised in that：Institute It is inorganic acid or lewis acid catalyst to state catalyst in step (1).
4. a kind of preparation method of Halogen melt-drip resistant inflaming retarding nylon 6 resin according to claim 3, it is characterised in that：Institute Inorganic acid is stated for hydrochloric acid, sulfuric acid, perchloric acid；Lewis acid catalyst is zinc chloride, sodium chloride, iron chloride, aluminium chloride, chlorination One kind in tin.
5. a kind of preparation method of Halogen melt-drip resistant inflaming retarding nylon 6 resin according to claim 2, it is characterised in that：Institute It is 6-72h to state the reaction time in step (1).
6. a kind of preparation method of Halogen melt-drip resistant inflaming retarding nylon 6 resin according to claim 2, it is characterised in that：Institute It is one kind in toluene, tetrahydrofuran, N, N dimethyl pyrrolidones, dioxane to state organic solvent in step (1).
7. a kind of preparation method of Halogen melt-drip resistant inflaming retarding nylon 6 resin according to claim 2, it is characterised in that：Institute It is water to state ring opening agent in step (2)；It is aminocaproic acid to help ring opening agent；End-capping reagent is adipic acid.
8. a kind of preparation method of Halogen melt-drip resistant inflaming retarding nylon 6 resin according to claim 2, it is characterised in that：Institute It is one in butyl titanate, isopropyl titanate, zinc acetate, manganese acetate, antimony oxide to state ester exchange catalyst in step (4) Kind.
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